CN1158628A - Biodegradable material comprising regenerative raw material and method of producing the same - Google Patents
Biodegradable material comprising regenerative raw material and method of producing the same Download PDFInfo
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- CN1158628A CN1158628A CN95195309A CN95195309A CN1158628A CN 1158628 A CN1158628 A CN 1158628A CN 95195309 A CN95195309 A CN 95195309A CN 95195309 A CN95195309 A CN 95195309A CN 1158628 A CN1158628 A CN 1158628A
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- butyl ester
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L21/00—Compositions of unspecified rubbers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L1/00—Compositions of cellulose, modified cellulose or cellulose derivatives
- C08L1/02—Cellulose; Modified cellulose
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L3/00—Compositions of starch, amylose or amylopectin or of their derivatives or degradation products
- C08L3/02—Starch; Degradation products thereof, e.g. dextrin
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L7/00—Compositions of natural rubber
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2995/00—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds
- B29K2995/0037—Other properties
- B29K2995/0059—Degradable
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/06—Biodegradable
Abstract
The invention concerns a biodegradable material comprising a matrix of latex, starch and polybetahydroxybutyrate and/or cellulose powder. This basic matrix can contain vegetable fillers, such as granulates of cereal grains or fibres of fibrous plants, for forming composite materials. The invention further concerns a method of preparing a biodegradable material, said method being characterized in that all the starting materials and the rubber in particular are in the comminuted form. These comminuted, for example, substantially granulated starting materials are mixed and plasticized in a screw-type extruder or in an injection moulding machine. The plasticized mass can be injected directly into a mould or extruded in the form of a strand which is processed to form granulates to be used as injection moulding material.
Description
The present invention relates to a kind of Biodegradable material and its manufacture method.Can be regarded as for Biodegradable material is these materials, and it is decomposed under the influence of environment and saboteur's activity influence.Existing known Biodegradable material, Peas is employed and makes base substance therein.Be known that in addition in common superpolymer to add starch, reach part and decompose so that make with this method.Only bury the starch share of putting into and be decomposed in this starch filled plastics, plastics substrate just splits into many aliquots like this.
The objective of the invention is a kind of material of suggestion, it be totally biodegradable and be applicable to formation to make filler and absorb wherein matrix material with point-like or fibrous particle.
The essentially consist that this task is used in suggestion in the claim 1 to 5 is solved.All these materials contain the rubber of 5-50% (weight) and the starch of 4-25% (weight).In this basal component, be mixed into the 3rd component of 10-50% share in promptly above-mentioned rubber and the starch.This component can be poly--beta-hydroxy-butyl ester or cellulose powder.The former obtains by the polymerization of beta-hydroxy-butanoic acid.It is that (Fa Zeneca) also can obtain commercial sign with " Biopol ".
Main ingredient by material of the present invention is a rubber.The preferred natural rubber that adopts is because it is a totally biodegradable.Also can adopt synthetic chloroprene rubber, it by the additive form that is adopted be at least the part or long storage time after under degradation condition degradable.The same basically powdered ingredients of starch powder and the third uniform distribution and at least only with the naked eye can not recognizing in base rubber.Has more or less elasticity by each share of claim 1 and 2 materials of the present invention according to rubber.Therefore, its manufacturing moulded piece that are applicable to more, even more important in this elasticity specific tenacity and stability.
For matrix material, depend on and bury the particle of putting, as having enough adhesive effects between point-like or fibrous particle and the substrate material.Mechanical property depends on the interface quality between particle and the matrix fatefully.It shows, can accept relative a large amount of filler and strongthener with 2 material by the method for GFK (glass fibre enhanced plastics) by claim 1.
To put thing be particulate state or the fibrous material of using regenerative raw materials as strengthening-burying by the present invention.Seed corn or the vegetable fibre of this raw material as pulverizing.The material that obtains is thus compared with 2 material with claim 1 and be it is characterized by bigger hardness and intensity.Therefore it be applicable to manufacturing bigger and planar moulded piece especially, as be used for the liner parts of Motor vehicles.In by material of the present invention, can add about 15% auxiliary substance at most.This material be can be regarded as it to material modification, and the mechanical property of material is not had tangible influence.This material for example is softening agent (as a tristearin), so that improve the plastification (see below) of raw material in pressure die-casting machine or extrusion machine.It also can be dyestuff and the mothproof material of stinging.
Another object of the present invention is that suggestion is by the manufacture method of material of the present invention.Rubber (uncrosslinked form) is the material of a kind of very heavy-gravity of being familiar with " like natural gum ", and Powdered or particulate material is difficult to add wherein.This is not always the case to artificial or natural rubber.Generally there is so-called book skin shape in the latter, and the latex from rubber producting plant obtains by water evaporates in the grown place for it.Powder is as using very high efficiency stapling machine and kneader just possible under high energy consumption if necessary in starch or Mierocrystalline cellulose or the coarse-grained particle adding rubber matrix.Advise now that by the present invention rubber adds with flocculent curd or particulate state.It and other component are easy to uniform mixing in simple mixing tank.Cotton-shaped and particulate state rubber obtains commercial.Heat in common screw extruder or in common pressure die-casting machine at the starting mixt that next operation steps will obtain like this and to plastify.Rubber wadding piece or particle can be heated to softening point temperature in the reason herein.Effect by extrusion machine or pressure die-casting machine screw rod mixes each component in the original stock up hill and dale.Usually heavy-gravity rubber tends to be cemented on the screw rod of above-mentioned machine and on the screw rod spatial inwall.This effect has hindered evenly mixing of component and has protected.The temperature rising that it also causes rubbing and increases and therefore make material to be machined.Temperature raises and to cause the variation do not expected, especially rubber hardening.But when mixing with said components in extrusion machine or pressure die-casting machine by rubber of the present invention wadding piece or rubber grain, this effect does not appear.Can prevent effectively by the following method that rubber from sticking on the screw rod and the inwall of machine on, each rubber particles wraps up one deck powder in plasticizing beginning step at least in the screw rod space.These one rubber grains connect to uniform base substance in next course of processing, and additive distributes wherein equably.But the result in the processing of the screw rod space of above-mentioned machine is a material plastifying, extruding and die casting.Next operation steps is this material or squeezes out or be cast into model as belt.The material belt that squeezes out to be pulverized first kind of situation, particle.Be to exist with particle by material of the present invention like this, in fact it can carry out intermediate storage arbitrarily for a long time and can be used for making die casting.Become model and obtain required module by material rheo-die-casting of the present invention in the latter case with direct method.
Raw material maintains the temperature at 170-180 ℃ in the plastification of screw rod spatial and shows it is favourable.Temperature is lower than the material that 170 ℃ of rubber can not fully soften and therefore add can not reach satisfied mixing.Here Temperature Influence also has an effect, the particularly crude substance of Jia Ruing in a not substantial variation of right and wrong and conversion of said temperature experience, and this performance to material neither not play an important role.Owing to this reason temperature can not surpass 180 too much.The main crude substance of being made up of starch, Mierocrystalline cellulose and protein has played variation at higher temperature section, and the material that obtains does not so have required performance.Particularly carbonaceous component such as Mierocrystalline cellulose or starch can burn or carbonization.Can accept filler share to 65% by material of the present invention.Can make thus and have a series of matrix material that varying strength and hardness level are arranged.
With making die casting, as the inner piece of basin, plate, dish and motor vehicle by matrix material of the present invention.The object of making is carried out outward appearance direct viewing and its performance of test.Also perparation of specimen spare, this is in order to measure various mechanical features parameters, as also explaining below.All these tests are reached a conclusion, if keep following composition (weight %), the material that can obtain to have special high-performance:
Rubber 10-30%
Yam starch 5-15%
Poly--beta-hydroxy butyl ester/Mierocrystalline cellulose 20-30%
Filler 20-60%
Subsidiary material maximum 10%
Can be with the particle and the fiber of each kind of plant as the filler of matrix material.The particularly particle of seed corn such as corn, rye and wheat.Can consider as the fiber of the fruit of Limonene flaxen fiber or kapok tree band shell as filamentary material.Also available lumber fibre or cotton fibre.
If the share of filler surpasses 60%, the material embrittlement that seems.Then contain rubber, potato and poly--beta-hydroxy butyl ester (to call PBHB in the following text) and cellulosic basic matrix no longer may make buries the particle of putting and is attached together, and their ability to accept is like transcendental.If the rubber share is reduced to below 10%, material also occurs and become fragile.Rubber content increases more than 30% elastic properties of materials and gives matrix material increasing performance, i.e. hardness and intensity.Filler content can be observed mechanical property greater than about 60% and degenerates.Especially tensile strength descends.Contain the additive of regenerative raw materials yes hydrophilic, promptly its absorbs moisture.Bury and put share more than 60% if contain regenerative raw materials, the swelling ability of material reaches the not degree of tolerable.Under this external high particle share when when plasticizing uniform distribution difficulty that becomes.Subsidiary material such as citric acid are stung agent (as preventing that home mouse and mouse sting) or tristearin should be limited in 10% as the softening agent total amount as mothproof, to prevent its side effect to mechanical property on sizable degree.
Adopting the cereal seed of explosion, is to make material obtain less density as the advantage of popcorn.In addition because pressure dome is contained in the heat-insulating property raising that makes material in the material.
The present invention is further illustrated by means of following example:
Embodiment 1
Natural rubber wadding piece 26%
Yam starch 6%
Popcorn 13%
Rye 26%
PBHB????????????????????26％
Citric acid 4%
Embodiment 2:
Natural rubber wadding piece 26%
Yam starch 12%
Oat 19%
Popcorn 12%
Dammar gum 12%
PBHB????????????????????19％
Citric acid 3%
Tristearin 2%
Jelly powder 2%
Embodiment 3
Natural rubber wadding piece 13%
Ma Lingzhu starch 13%
Oat 13%
Rye 26%
PBHB??????????????20％
Tristearin 3%
Citric acid 3%
Jelly powder 2%
Popcorn 7%
In the component of pressing embodiment 1-3, add tristearin as softening agent." matrix " is made up of rubber, Ma Lingzhu starch and PBHB in this component.Yam starch is the main ingredient of matrix in above-mentioned and the embodiment that also exemplifies below, particularly owing to the reason of cost is used it.Also can adopt other starch such as rice, corn or cereal starch.
By the following manufacturing of carrying out by material of the present invention:
Flocculent curd or granular rubber mix in a common mixing machine uniformly with all the other components.At least yam starch becomes fine powder or powder material at this, and filler such as corn, rye, oat become particulate state.Mix back latex-flocculent curd uniform distribution or in contrast in remaining component.Ready like this starting mixt plastifies in 75 tons of pressure die-casting machines.It is added in the feed hopper of machine for this reason, enter the screw rod space of machine by this funnel.Machine is performed such heating, and promptly the material that exists in the screw rod space has 170 ℃-180 temperature.At this temperature range rubber softening.Rotation by screw rod makes filler expect to join in the rubber matrix to go with auxiliary.The crude substance that adds in above-mentioned temperature also changes.But test is not carried out at this.But can infer, be not unessential to the effect of crude substance to the performance of later material in screw rod spatial temperature.Certainly at least the rubber wadding piece of heated condition viscosity screw rod or on screw rod spatial inwall fixed can preventing with this method, be about to rubber wadding piece with starch or other powdered components parcel, material finished after 1 minute the latest in the plasticizing of screw rod spatial.
With various moulded piece of plastifying material die casting such as basin, dish and sample.Sample is used for by the test determination mechanical features parameter that illustrates below.
Use Z1 below, the composition of Z2 and Z3 mark embodiment 1-3.
Press the pliability test of DIN53452:
Table 1:
Bending strength (N/mm
2)
| Sample number | ????Z1 | ????Z2 | ????Z3 |
| ????1 | ????23,38 | ????22,22 | ????40,42 |
| ????2 | ????25,09 | ????21,17 | ????43,17 |
| ????3 | ????23,39 | ????21,55 | ????37,36 |
| ????4 | ????23,86 | ????19,43 | ????41,29 |
| ????5 | ????20,91 | ????19,54 | ????38,62 |
| Average bending strength | ????23,33 | ????20,78 | ????40,17 |
Table 2: the elongation when maximum, force (%)
| Sample number | ????Z1 | ????Z2 | ????Z3 |
| ????1 | ????2,35 | ????3,14 | ????3,21 |
| ????2 | ????3,00 | ????2,36 | ????3,14 |
| ????3 | ????2,47 | ????2,57 | ????2,86 |
| ????4 | ????2,23 | ????2,71 | ????3,08 |
| ????5 | ????1,68 | ????2,28 | ????3,05 |
| Average elongation during maximum pull | ????2,35 | ????2,61 | ????3,07 |
For carrying out being with the average cross section at right angle by the pliability test employing of table 1 and 2 is the sample of 416mm * 9.89mm.Test speed is 2mm/ minute.
In pliability test, measure Young's modulus by DIN 53457:
With mean thickness is that the sample of 4.1mm and width average out to 9.9mm is tested.
Table 3: Young's modulus (N/mm
2)
| Sample number | ????Z1 | ????Z2 | ????Z3 |
| ????1 | ????1821,2 | ????1270,1 | ????1749,9 |
| ????2 | ????1707,3 | ????1472,5 | ????1844,7 |
| ????3 | ????1725,0 | ????1177,3 | ????1881,4 |
| Average E modulus | ????1751,2 | ????1306,6 | ????1825,3 |
The mensuration of longitudinal dilatation coefficient:
Be of a size of the sample of 15 * 10.5 * 117mm by Z1 and Z2 die casting.In rate of heating is that 120k/h measures the longitudinal dilatation coefficient.All three samples show suitable constant expansion curve to about 80 ℃.The coefficient of expansion in the constant scope is listed in table 4.
Table 4: the coefficient of expansion (10-5K-1):
| ????Z1 | ????Z2 | ????Z3 | |
| ????12,5 | ????13,9 | ????12 |
Press DIN 53735 and measure melting index:
This test is only carried out with the composition material by embodiment 1 (Z1).Probe temperature is 190 ℃.The sample of fritter is placed on the test cylinder neutralization is heated for measuring melting index.One nozzle is arranged below the test cylinder, and the remollescent material becomes strip to squeeze out from nozzle by a pressure punch (load 2.61kp) that is contained in the cylinder.Test result MFI (melt flow index) is 2.59g/10 minute.
Press DIN 75200 and measure combustionproperty:
The mensuration of combustionproperty particularly has requirement to the material that is used for the Motor vehicles liner.Deposit in standard climate condition (23 ℃, air themperature is 50% relatively) with pressure casting method manufacturing sheet material with above 48 hours.Sheet material is of a size of 139mm * 79mm * 3mm.This sheet material is lighted and is measured burning extent (Brenn strecke) and combustion time on the edge.To 5 samples of every composition (Z1 to Z3) test, following table is average combustionvelocity and a maximum combustion speed of having concluded each five sample.
Table 5: combustionproperty (average and maximum combustion speed mm/ divides expression)
| ????Z1 | ????Z2 | ????Z3 | |
| Average combustionvelocity | ????33,4 | ????18,2 | ????44,4 |
| Maximum combustion speed | ????39,8 | ????19,9 | ????49,0 |
Density measurement:
For measuring the die casting sheet material weighing of density with 2.9mm * 79mm * 139mm, precision is to 0.001g.Measure the volume of sheet material and calculate density from the volume and weight value.
Table 6: density (g/cm
3)
| ????Z1 | ????Z2 | ????Z3 | |
| Mean density | ????1,24 | ????1,23 | ????1,20 |
Press DIN 52351 and measure absolute moisture content:
To consist of Z1 for measuring relative humidity, the sheet material of Z2 and Z3 (23 ℃, relative air humidity is 50%) under the standard climate condition was deposited 48 hours and was measured then it and deposits afterwards and the drying regime increase of weight/power ratio mutually in wet air and water.Its result is summarized in table 7.
Table 7: average absolute moisture content (%)
| ????Z1 | ????Z2 | ????Z3 | |
| The average absolute moisture content | ????0,21 | ????0,81 | ????0,43 |
Measure suction and swelling according to DIN 52351
Originally deposited 48 hours at standard climate (23 ℃, relative air humidity is 50%) for measuring the sheet material that suction and swelling will consist of Z1, Z2 and Z3 material.Part sample is deposited and 24,48 in wet empty institute (relative humidity is 95%, 55 ℃), the mean thickness that the mensuration percentage value is represented after 72,96 hours and the change of quality.
Table 8: the variation of mean thickness and average quality
(variation in thickness Δ d and quality change Δ m represent with %) deposits in wet air and water
| Δ | ?????Z1 | ?????Z2 | ?????Z3 | |
| After Δ d/ Δ m deposits in air | ????24h | ??0,00/0,61 | ??1,54/1,25 | ??0,96/0,86 |
| ????48h | ??0,27/0,68 | ??1,54/1,25 | ??0,96/0,94 | |
| ????72h | ??0,83/0,68 | ??1,54/1,25 | ??0,96/94 | |
| ????96h | ??????- | ??????- | ?????- | |
| After Δ d/ Δ m deposits in water | ????24h | ??11,24/2,14 | ??15,85/3,76 | ??2,25/0,96 |
| ????48h | ??13,61/2,83 | ??15,85/5,12 | ??3,46/1,52 | |
| ????72h | ??14,87/3,56 | ??16,69/6,35 | ??3,46/1,86 | |
| ????96 | ??14,87/4,19 | ??16,69/7,33 | ??3,46/2,19 | |
Press DIN 53455 and in tension test, measure tension force and elongation:
By forming Z1-Z3 manufacturing mean thickness is that 4mm and width average are the sample rod of 10mm (master bar Nr.3).The mensuration of tensile strength and elongation once test speed 5mm/min (minute) and another time carry out at 50mm/min.Elongation-with the deviation of DIN standard-measure from clamping jaw variable in distance.Test-results is summarized in table 9 and 10.
Table 9: tensile strength (N/mm
2)
| Sample number | ???????????????Z1 | ???????????????Z2 | ???????????????Z3 | |||
| ?5mm/min | ?50mm/min | ?5mm/min | ?50mm/min | ?5mm/min | ?50mm/min | |
| ????1 | ??5,92 | ??7,94 | ??14,11 | ??14,69 | ??12,10 | ??14,01 |
| ????2 | ??6,79 | ??6,65 | ??13,46 | ??10,98 | ??11,68 | ??16,86 |
| ????3 | ??6,64 | ??7,04 | ??10,13 | ??13,35 | ??11,73 | ??19,48 |
| ????4 | ??6,83 | ??7,84 | ??11,18 | ??13,01 | ??11,43 | ??13,98 |
| ????5 | ??6,57 | ??12,05 | ??14,05 | ??16,49 | ??11,10 | ??13,42 |
| Average tensile strength | ??6,55 | ??8,30 | ??12,57 | ??13,70 | ??11,61 | ??15,55 |
Table 10: the elongation when maximum, force (%)
| Sample number | ???????????????Z1 | ???????????????Z2 | ????????????????Z3 | |||
| ?5?mm/min | ?50mm/min | ?5mm/min | ?50mm/min | ?5mm/min | ?50mm/min | |
| ????1 | ??6,54 | ??8,54 | ??9,22 | ??9,16 | ??11,84 | ??13,46 |
| ????2 | ??6,86 | ??7,30 | ??7,86 | ??8,76 | ??11,92 | ??14,04 |
| ????3 | ??7,16 | ??8,86 | ??8,00 | ??6,80 | ??12,00 | ??15,84 |
| ????4 | ??7,92 | ??8,66 | ??8,78 | ??7,60 | ??11,32 | ??12,62 |
| ????5 | ??7,18 | ??8,66 | ??8,76 | ??10,10 | ??12,56 | ??10,84 |
| Average elongation when maximum, force | ??7,13 | ??8,44 | ??8,52 | ??8,48 | ??11,93 | ??13,36 |
Except the extremely different composition of the foregoing description 1-3 external application is made other material and is processed with casting die.Make placing, basin and tabular die casting thus.Component and the content range of this embodiment are summarized in table 11.
Table 11: embodiment 4-19 (content data is represented with weight %)
| Embodiment | ||||||||||||||||
| ??4 | ??5 | ??6 | ??7 | ??8 | ??9 | ??10 | ??11 | ??12 | ??13 | ??14 | ??15 | ??16 | ??17 | ??18 | ??19 | |
| Matrix, total amount | ??50 | ??70 | ??33,4 | ??60 | ??80 | ??80 | ??80 | ??75 | ??63,4 | ??65,8 | ??68,7 | ??82,5 | ??60 | ??85 | ??66,6 | ??53,5 |
| Wadding piece rubber | ??10 | ??20 | ??6,3 | ??10 | ??30 | ??40 | ??50 | ??25 | ??6,7 | ??9,9 | ??21,5 | ??8 | ??6 | ??25 | ??8,3 | ??4,1 |
| Yam starch | ??10 | ??10 | ??6,3 | ??- | ??10 | ??20 | ??20 | ??- | ??10 | ??6,2 | ??4,3 | ??5,3 | ??4 | ??10 | ??8,3 | ??4,1 |
| ????″PBHB″ | ??30 | ??20 | ??20,8 | ??10 | ??20 | ??- | ??10 | ??25 | ??46,7 | ??- | ??- | ??53,2 | ??26 | ??50 | ??25 | ??41,2 |
| Cellulose powder | ??- | ??20 | ??- | ??40 | ??20 | ??20 | ??- | ??25 | ??- | ??49,7 | ??42,9 | ??16 | ??24 | ??- | ??25 | ??4,1 |
| Filler, total amount | ??40 | ??30 | ??56,3 | ??40 | ??20 | ??20 | ??20 | ??25 | ??36,8 | ??31 | ??21,5 | ??5,3 | ??38 | ??15 | ??33,4 | ??34,1 |
| Popcorn | ??- | ??- | ??- | ??- | ??- | ??- | ??- | ??- | ??6,7 | ??9,3 | ??4,3 | ??- | ??- | ??- | ??- | ??- |
| Rye | ??- | ??- | ??- | ??- | ??- | ??- | ??- | ??- | ??10 | ??3,1 | ??- | ??- | ??18 | ??- | ??- | ??- |
| Oat | ??- | ??- | ??- | ??- | ??- | ??- | ??- | ??- | ??6,7 | ??- | ??- | ??- | ??- | ??- | ??- | ??- |
| Corn | ??40 | ??30 | ??56,3 | ??40 | ??20 | ??20 | ??20 | ??25 | ??6,7 | ??12,4 | ??4,3 | ??5,3 | ??16 | ??15 | ??16,7 | ??21,8 |
| Soya bean | ??- | ??- | ??- | ??- | ??- | ??- | ??- | ??- | ??6,7 | ??6,2 | ??- | ??- | ??4 | ??- | ??16,7 | ??8,2 |
| The slabstone powder | ??- | ??- | ??- | ??- | ??- | ??- | ??- | ??- | ??- | ??- | ??12,9 | ??- | ??- | ??- | ??- | ??4,1 |
| Auxiliary material total amount | ??10 | ??- | ??10,5 | ??- | ??- | ??- | ??- | ??- | ??- | ??3,1 | ??9,9 | ??12,2 | ??2 | ??- | ??- | ??12,3 |
| Citric acid | ??- | ??- | ??- | ??- | ??- | ??- | ??- | ??- | ??- | ??3,1 | ??1,3 | ??1,6 | ??- | ??- | ??- | ??4,1 |
| Dammar gum | ??10 | ??- | ??6,3 | ??- | ??- | ??- | ??- | ??- | ??- | ??- | ??4,3 | ??5,3 | ??1 | ??- | ??- | ??4,1 |
| Tristearin | ??- | ??- | ??- | ??- | ??- | ??- | ??- | ??- | ??- | ??- | ??4,3 | ??5,3 | ??- | ??- | ??- | ??4,1 |
| Jelly powder | ??- | ??- | ??4,2 | ??- | ??- | ??- | ??- | ??- | ??- | ??- | ??- | ??- | ??1 | ??- | ??- | ??- |
Claims (16)
1. biodegradable material is characterized in that following composition (weight %)
Rubber 5-50%
Starch 4-25%
Poly--beta-hydroxy butyl ester 10-50%
Subsidiary material 0-15%
2. Biodegradable material is characterized in that following composition (weight %)
Rubber 5-50%
Starch 4-25%
Cellulose powder 10-50%
Subsidiary material 0-15%
3. contain thermoplastic matrix and wherein bury the particle of the regenerative raw materials of putting-or the biodegradable composite material of bat wool, it is characterized in that matrix is made up of following material
Rubber 5-50% (weight)
Starch 4-25% (weight)
Poly--beta-hydroxy butyl ester 10-50% (weight)
4. contain thermoplastic matrix and wherein bury the particle of the regenerative raw materials of putting-or the biodegradable composite material of bat wool, it is characterized in that matrix is made up of following material
Rubber 5-50% (weight)
Starch 4-25% (weight)
Cellulose powder 10-50% (weight)
5. contain thermoplastic matrix and wherein bury the particle of the regenerative raw materials of putting-and the biodegradable composite material of bat wool, it is characterized in that matrix is made up of following material
Rubber 5-50% (weight)
Starch 4-25% (weight)
Poly--beta-hydroxy butyl ester and Mierocrystalline cellulose
Mixture 10-50% (weight)
6. by the material of one of claim 3,4 and 5 item, it is characterized in that the share of filler mostly is 65% most.
7. by the material of claim 6, it is characterized in that following composition (weight %)
Rubber 10-30%
Yam starch 5-15%
Poly--beta-hydroxy butyl ester and/or
Mierocrystalline cellulose 20-30%
Filler 25-60%
Subsidiary material maximum 10%
8. by one of claim 3-7 material, it is characterized in that filler is the seed or the vegetable fibre of cereal.
9. by one of claim 3-8 raw material, it is characterized in that, is to make filler with the particle of the seed corn of explosion.
10. by one of claim 1-9 material, it is characterized in that rubber is natural rubber.
11. by the material of claim 10, it is characterized in that, by following the composition (weight %):
Natural rubber 26%
Yam starch 6%
Popcorn 13%
Rye 26%
Poly--beta-hydroxy butyl ester 25%
Citric acid 4%
12. the material by claim 10 is characterized in that, by following the composition (weight %)
Natural rubber 13%
Yam starch 13%
Oat 13%
Rye 26%
Poly--beta-hydroxy butyl ester 20%
Tristearin 3%
Citric acid 3%
Gelatin powder 2%
Popcorn 7%
13. by the material of claim 10, it is characterized in that, by following the composition (weight %):
Natural rubber 19%
Yam starch 12%
Oat 19%
Popcorn 12%
Dammar gum 12%
Poly--beta-hydroxy butyl ester 19%
Citric acid 3%
Tristearin 2%
Jelly powder 2%
14. the manufacture method by one of claim 1-3 prong material is characterized in that following steps are arranged
A) with raw material, poly--β-hydroxy butyl ester as starch, filler and auxiliary material are prepared to the shape of pulverizing, i.e. powder or particle;
B) rubber is prepared to wadding piece or particulate state;
C) raw material is evenly mixed mutually;
D) starting mixt that obtains like this plastifies at screw extruder or pressure die-casting machine under heating;
E) plastifying material is discharged and is made it cooling from extrusion machine or in the pressure die-casting machine.
15. by the method for claim 14, it is characterized in that, at d set by step) during plasticizing temperature maintenance at 170-180 ℃.
16. the method by claim 15 is characterized in that the material that squeezes out carries out granulation and is used to make compression moulded element as raw material.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE9413921 | 1994-08-27 | ||
| DEG9413921.0U | 1994-08-27 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1158628A true CN1158628A (en) | 1997-09-03 |
Family
ID=6912965
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN95195309A Pending CN1158628A (en) | 1994-08-27 | 1995-08-28 | Biodegradable material comprising regenerative raw material and method of producing the same |
Country Status (16)
| Country | Link |
|---|---|
| US (1) | US5719203A (en) |
| EP (1) | EP0777699B1 (en) |
| JP (1) | JP3447298B2 (en) |
| KR (1) | KR970705606A (en) |
| CN (1) | CN1158628A (en) |
| AT (1) | ATE185828T1 (en) |
| AU (1) | AU3473795A (en) |
| BR (1) | BR9508812A (en) |
| CA (1) | CA2197981C (en) |
| CZ (1) | CZ53697A3 (en) |
| DE (1) | DE59507100D1 (en) |
| DK (1) | DK0777699T3 (en) |
| ES (1) | ES2140702T3 (en) |
| MX (1) | MX9701133A (en) |
| PL (1) | PL181959B1 (en) |
| WO (1) | WO1996006886A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2023103114A1 (en) * | 2021-12-10 | 2023-06-15 | 王素贞 | Environmentally-friendly fully-biodegradable plastic and sheet product |
Families Citing this family (19)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH08109278A (en) * | 1994-10-12 | 1996-04-30 | Hideo Kakigi | Molded foam, raw material for molded foam, and production of molded foam |
| DE19543635A1 (en) * | 1995-11-23 | 1997-05-28 | Hp Chemie Pelzer Res & Dev | Composite materials made from polyhydroxy fatty acids and fiber materials |
| DE19705280C1 (en) * | 1997-02-12 | 1998-03-05 | Daimler Benz Ag | Fibre-reinforced plastics moulding used in commercial, passenger and rail vehicles and aircraft |
| EP0966500A4 (en) * | 1997-02-14 | 2000-10-11 | Foster Miller Inc | Biodegradable polymers |
| DE19802718C2 (en) * | 1998-01-24 | 2002-02-21 | Hubert Loick Vnr Gmbh | Thermoplastic, compostable polymer composition |
| US6074587A (en) | 1998-02-13 | 2000-06-13 | Cs Enviromental Technology Ltd. | Degradable container and a method of forming same |
| EP0943410A1 (en) * | 1998-03-19 | 1999-09-22 | Heinrich Wolf | Single stage process for manufacturing a decorative article from regenerable raw material |
| CN1384853A (en) * | 1999-09-22 | 2002-12-11 | Econeer株式会社 | Composition for molding articles and method for preparing molded articles therefrom |
| DE10027905A1 (en) * | 2000-06-06 | 2001-12-13 | Bayer Ag | Biodegradable molding composition, useful for the production of plant covers, disposable cutlery, casings or packaging, comprises a biodegradable polymer and a mineral and/or a renewable material, |
| US7402618B2 (en) * | 2000-11-23 | 2008-07-22 | Hao Xu | Biodegradable composition for the preparation of tableware, drink container, mulching film and package and method for preparing the same |
| CN1121452C (en) * | 2000-11-23 | 2003-09-17 | 许浩 | Formular and preparing process of environment protection type biodegradable dinner set |
| AU2003241846A1 (en) * | 2002-05-24 | 2003-12-12 | Nexsol Technologies, Inc. | Biodegradable compound and preparation method thereof, and molded material made of the same and molding method thereof |
| WO2004072165A1 (en) * | 2003-02-06 | 2004-08-26 | Don-B Corporation | Additive for rubber elastomers |
| WO2004072118A2 (en) * | 2003-02-06 | 2004-08-26 | Don-B Corporation | Additive for rubber elastomers |
| JPWO2005044922A1 (en) * | 2003-11-07 | 2007-11-29 | 株式会社ネイチャートラスト | Biodegradable / disintegrating resin composition |
| DE102006041308A1 (en) * | 2006-09-01 | 2008-03-20 | Center For Abrasives And Refractories Research & Development C.A.R.R.D. Gmbh | Method for introducing hard materials into a tire tread |
| JP5845721B2 (en) * | 2011-08-25 | 2016-01-20 | 日本電気株式会社 | Moisture measuring method and moisture measuring device |
| DE102018132738A1 (en) * | 2018-12-18 | 2020-06-18 | Georg-August-Universität Göttingen Stiftung Öffentlichen Rechts | Use of expanded and hydrophobic popcorn for the production of three-dimensional molded parts |
| DE102019204050A1 (en) * | 2019-03-25 | 2020-10-01 | Timm Oberhofer | Household goods made from biodegradable plastic and predominantly cellulose |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2900402B2 (en) * | 1989-05-26 | 1999-06-02 | エヌオーケー株式会社 | Biodegradable rubber composition |
| DE4025523A1 (en) * | 1990-08-11 | 1992-02-13 | Werner Georg Munk | ROTATABLE CONTAINER, METHOD FOR THE PRODUCTION AND USE THEREOF |
| FR2697259B1 (en) * | 1992-10-28 | 1996-06-07 | Roquette Freres | BIODEGRADABLE THERMOFORMABLE COMPOSITIONS, THEIR PREPARATION PROCESS AND THEIR USE FOR OBTAINING THERMOFORMED ARTICLES. |
| DE59308261D1 (en) * | 1992-12-19 | 1998-04-16 | Jung H Metraplast Gmbh | USE OF A COMPOSITION FOR A MATERIAL IN INJECTION MOLDING PROCESS |
-
1995
- 1995-08-28 BR BR9508812A patent/BR9508812A/en not_active IP Right Cessation
- 1995-08-28 MX MX9701133A patent/MX9701133A/en unknown
- 1995-08-28 DE DE59507100T patent/DE59507100D1/en not_active Expired - Lifetime
- 1995-08-28 CZ CZ97536A patent/CZ53697A3/en unknown
- 1995-08-28 JP JP50848896A patent/JP3447298B2/en not_active Expired - Lifetime
- 1995-08-28 KR KR1019970701185A patent/KR970705606A/en not_active Application Discontinuation
- 1995-08-28 PL PL95318879A patent/PL181959B1/en unknown
- 1995-08-28 DK DK95931213T patent/DK0777699T3/en active
- 1995-08-28 AU AU34737/95A patent/AU3473795A/en not_active Abandoned
- 1995-08-28 AT AT95931213T patent/ATE185828T1/en not_active IP Right Cessation
- 1995-08-28 CN CN95195309A patent/CN1158628A/en active Pending
- 1995-08-28 WO PCT/EP1995/003388 patent/WO1996006886A1/en not_active Application Discontinuation
- 1995-08-28 EP EP95931213A patent/EP0777699B1/en not_active Expired - Lifetime
- 1995-08-28 CA CA002197981A patent/CA2197981C/en not_active Expired - Fee Related
- 1995-08-28 US US08/776,905 patent/US5719203A/en not_active Expired - Lifetime
- 1995-08-28 ES ES95931213T patent/ES2140702T3/en not_active Expired - Lifetime
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2023103114A1 (en) * | 2021-12-10 | 2023-06-15 | 王素贞 | Environmentally-friendly fully-biodegradable plastic and sheet product |
Also Published As
| Publication number | Publication date |
|---|---|
| CA2197981A1 (en) | 1996-03-07 |
| ATE185828T1 (en) | 1999-11-15 |
| DK0777699T3 (en) | 2000-04-17 |
| KR970705606A (en) | 1997-10-09 |
| EP0777699A1 (en) | 1997-06-11 |
| BR9508812A (en) | 1997-12-23 |
| AU3473795A (en) | 1996-03-22 |
| WO1996006886A1 (en) | 1996-03-07 |
| PL181959B1 (en) | 2001-10-31 |
| DE59507100D1 (en) | 1999-11-25 |
| JPH10504851A (en) | 1998-05-12 |
| CZ53697A3 (en) | 1997-07-16 |
| CA2197981C (en) | 2002-11-12 |
| EP0777699B1 (en) | 1999-10-20 |
| ES2140702T3 (en) | 2000-03-01 |
| MX9701133A (en) | 1997-10-31 |
| JP3447298B2 (en) | 2003-09-16 |
| PL318879A1 (en) | 1997-07-07 |
| US5719203A (en) | 1998-02-17 |
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